Bulk Fe-rich Fe-B alloy melts were undercooled and even hypercooled by adopting molten glass purification combined with high-frequency vacuum melting and cyclical superheating. The cooling curves of eutectic and off-eutectic alloys upon solidification which were subjected to different undercoolings are described and compared. Then systematic investigations for structural evolution, including a morphological change of the primary phase and transformation mechanisms for hypoeutectic, hypereutectic and eutectic alloys were carried out. In particular, for the eutectic Fe83B17 alloy melt subjected to hypercoolings of 300-460 K, phase selection between the stable Fe2B and the metastable Fe3B was found and described. A bulk Fe-B eutectic structure with metastable Fe3B can be directly solidified from the hypercooled melt and then be preserved at room temperature, provided the undercooling exceeds 386K. These phenomena were also observed for some hypereutectic alloys with some undercooling. On these bases, an evolution map of the eutectic zone as a function of composition and temperature was deduced.(c) 2008 Elsevier B.V. All rights reserved.